Electronic Substitution Effect on the Ground and Excited State Properties of Indole Chromophore: A Computational Study.

Indole, being the main chromophore of amino acid tryptophan and several other biologically relevant molecules like serotonin, melatonin, has prompted considerable theoretical and experimental interest. The current work focuses on the investigation of substitution effect on the ground and excited electronic states of indole using computational quantum chemistry. Having three close-lying excited electronic states, the vibronic coupling effect becomes extremely important yet challenging for the photophysics and photochemistry of indole. Here, we have evaluated the performance of time-dependent density functional theory against available experimental and ab initio results from the literature. The electronic effects on the excited states of indole and indole derivatives e. g. tryptophan, serotonin and melatonin are reported. A bathochromic shift has been observed in the absorption spectrum for the La state. The absorption wavelength increases in the order of indole

Nonempirical Simulations of Inhomogeneous Broadening of Electronic Transitions in Solution: Predicting Band Shapes in One- and Two-Photon Absorption Spectra of Chalcones.

We have examined several approaches relying on the Polarizable Embedding (PE) scheme to predict optical band shapes for two chalcone molecules in methanol solution. The PE-TDDFT and PERI-CC2 methods were combined with molecular dynamics simulations, where the solute geometry was kept either as rigid, flexible or partly-flexible (restrained) body. The first approach, termed RBMD-PE-TDDFT, was employed to estimate the inhomogeneous broadening for subsequent convolution with the vibrationally-resolved spectra of the molecule in solution determined quantum-mechanically (QM). As demonstrated, the RBMD-PE-TDDFT/QM-PCM approach delivers accurate band widths, also reproducing their correct asymmetric shapes. Further refinement can be obtained by the estimation of the inhomogeneous broadening using the RBMD-PERI-CC2 method. On the other hand, the remaining two approaches (FBMD-PE-TDDFT and ResBMD-PE-TDDFT), which lack quantum-mechanical treatment of molecular vibrations, lead to underestimated band widths. In this study, we also proposed a simple strategy regarding the rapid selection of the exchange-correlation functional for the simulations of vibrationally-resolved one- and two-photon absorption spectra based on two easy-to-compute metrics.

Vibrationally resolved electronic circular dichroism and circularly polarized luminescence spectra of a boron-fused double helicene: A theoretical study.

In this work, we present the theoretical study of the vibrationally resolved absorption (ABS), electronic circular dichroism (ECD), emission (EMI), and circularly polarized luminescence (CPL) spectra of a boron-fused double helicene, with a detailed and complete discussion of the alternative possible approximate methods. Given the fact that few examples of CPL calculations exist, the potential energy surfaces (PESs) have been constructed and compared with Adiabatic (AH) and Vertical Hessian (VH) models. All the vibronic calculations have accounted for Duschinsky mixings, Franck-Condon (FC) effect and Herzberg-Teller (HT) contribution. Moreover, different HT expansions have been checked and compared, by computing the derivatives of the electric and magnetic dipole transition moments around the equilibrium geometries of the initial and final states. Our results show that both AH and VH models have well reproduced the experimental vibronic structures and VH model shows a better performance in the simulation of spectral lineshapes. They also show that HT effects dominate the shapes of EMI and CPL, tuning the relative heights of the different vibronic peaks, improving the agreement with the experiment for EMI. Moreover, HT effects are the main reason for the mirror-symmetry breaking between ECD and CPL spectra. Furthermore, interesting interference effects between FC and HT contributions have also been addressed.